Screening of transition metal and boron atoms co-doped graphdiyne catalysts for electrocatalytic urea synthesis.

Electrocatalytic CN coupling using nitrogen (N) and carbon dioxide (CO) as precursors offers a promising alternative for urea production under mild conditions, compared to traditional synthesis approaches. However, the design and screening of extremely efficient electrocatalysts remains a significant challenge in this field. Hence, we propose a systematic approach to screen efficient double-atom catalysts (DACs) with both metal and boron active sites, employing density functional theory (DFT). A comprehensive evaluation of 27 potential catalysts were performed, taking into account their stability, co-adsorption of N and CO, as well as the potential-determining step (PDS) involved urea formation. The calculated results show that co-doped graphdiyne with CrB and MnB double atoms (CrB@GDY and MnB@GDY) emerge as potential electrocatalysts for urea production, displaying thermodynamic energy barriers of 0.41 eV and 0.66 eV, respectively. More importantly, these two DACs can significantly suppress the ammonia (NH) and C products formation. Furthermore, a catalytic activity relationship between the d-band centers of the DACs and urea production performance were established. This study not only forecasts two promising DACs for subsequent experimental work but also establishes a theoretical framework for the evaluation of DACs in electrocatalytic urea synthesis.